JP5527667B2 - Pyrroline-based nitroxide polymer and battery using the same - Google Patents
Pyrroline-based nitroxide polymer and battery using the same Download PDFInfo
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- JP5527667B2 JP5527667B2 JP2011503792A JP2011503792A JP5527667B2 JP 5527667 B2 JP5527667 B2 JP 5527667B2 JP 2011503792 A JP2011503792 A JP 2011503792A JP 2011503792 A JP2011503792 A JP 2011503792A JP 5527667 B2 JP5527667 B2 JP 5527667B2
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- Prior art keywords
- pyrroline
- active material
- electrode active
- electrode
- polymer
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- UKZCGMDMXDLAGZ-UHFFFAOYSA-M magnesium;2-methylpropane;bromide Chemical compound [Mg+2].[Br-].C[C-](C)C UKZCGMDMXDLAGZ-UHFFFAOYSA-M 0.000 description 1
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、ピロリン系ニトロキシド重合体、当該重合体を含有する電極活物質および当該電極活物質を用いた電池に関する。 The present invention relates to a pyrroline-based nitroxide polymer, an electrode active material containing the polymer, and a battery using the electrode active material.
ノート型パソコンや携帯電話等の急速な市場拡大に伴い、これらに用いられるエネルギー密度の高い小型大容量二次電池への要求が高まっている。この要求に応えるために、リチウムイオン等のアルカリ金属イオンを荷電担体としてその電荷授受に伴う電気化学反応を利用した二次電池が開発されている。中でもリチウムイオン二次電池は、エネルギー密度が高く、安定性に優れた大容量二次電池として種々の電子機器に利用されている。このようなリチウムイオン二次電池は、一般に、活物質として正極にリチウム含有遷移金属酸化物を、負極に炭素を用いたものであり、これら活物質へのリチウムイオンの挿入、脱離反応を利用して充放電を行っている。 With the rapid market expansion of notebook personal computers and mobile phones, there is an increasing demand for small high-capacity secondary batteries with high energy density used for these. In order to meet this demand, a secondary battery using an alkali metal ion such as lithium ion as a charge carrier and utilizing an electrochemical reaction accompanying charge transfer has been developed. Among these, lithium ion secondary batteries are used in various electronic devices as high-capacity secondary batteries having high energy density and excellent stability. Such a lithium ion secondary battery generally uses a lithium-containing transition metal oxide as a positive electrode as an active material and carbon as a negative electrode, and utilizes insertion and desorption reactions of lithium ions into these active materials. Charging and discharging.
近年、より大容量化を目的に、電極反応に直接寄与する電極活物質としてラジカル化合物を利用した二次電池が提案されている。特許文献１には、正極、負極の少なくとも一方の活物質としてラジカル化合物を含有することを特徴とする二次電池が公開されている。また、特許文献２には、ニトロキシル化合物を正極中に含有する蓄電デバイスが公開されている。この蓄電デバイスは、電極反応が速いため大電流で充放電ができるとされている。 In recent years, secondary batteries utilizing radical compounds as electrode active materials that directly contribute to electrode reactions have been proposed for the purpose of increasing capacity. Patent Document 1 discloses a secondary battery including a radical compound as an active material of at least one of a positive electrode and a negative electrode. Patent Document 2 discloses an electricity storage device containing a nitroxyl compound in a positive electrode. This electricity storage device is said to be able to charge and discharge with a large current because of its fast electrode reaction.
しかしながら、特許文献１に記載の正極、負極の少なくとも一方の活物質がラジカル化合物を含有することを特徴とする二次電池や、特許文献２に記載の安定ラジカルを含むニトロキシル化合物を用いた蓄電デバイスは、繰り返し充放電後の容量低下の面において改善の余地があった。 However, a secondary battery in which at least one of the positive electrode and the negative electrode active material described in Patent Document 1 contains a radical compound, and an electricity storage device using a nitroxyl compound containing a stable radical described in Patent Document 2 However, there was room for improvement in terms of capacity reduction after repeated charge and discharge.
本発明は、大きな電流を取り出すことができ、かつ、繰り返し充放電を行っても容量の低下が少ない電池の電極材料として用いられるピロリン系ニトロキシド重合体、当該重合体を含有する電極活物質および当該電極活物質を用いた電池を提供することを目的とする。 The present invention is a pyrroline-based nitroxide polymer that can be used as an electrode material for a battery that can take out a large current and has little decrease in capacity even after repeated charge and discharge, an electrode active material containing the polymer, and the It aims at providing the battery using an electrode active material.
本発明は、一般式（１）：
また、本発明は、前記ピロリン系ニトロキシド重合体を含有する電極活物質に関する。
さらに、本発明は、前記電極活物質を用いた電池に関する。
以下に本発明を詳細に説明する。The present invention relates to a general formula (1):
The present invention also relates to an electrode active material containing the pyrroline nitroxide polymer.
Furthermore, the present invention relates to a battery using the electrode active material.
The present invention is described in detail below.
本発明に係るピロリン系ニトロキシド重合体は、下記一般式（１）で表されるビニル基を有するピロリン系ニトロキシド化合物を重合して得られるものである。
一般式（１）で表されるピロリン系ニトロキシド化合物は、例えば、下記式（２）に示すように、３−カルバモイル−２，２，５，５−テトラメチルピロリン−１−オキシルを用いる方法（ＣＡＮ．Ｊ．ＣＨＥＭ．，６４，１４８２−１４９０（１９８６））により製造することができる。具体的には、水酸化ナトリウム水溶液等を用いて３−カルバモイル−２，２，５，５−テトラメチルピロリン−１−オキシルを加水分解して３−カルボキシ−２，２，５，５−テトラメチルピロリン−１−オキシルとし、次に、アルゴンガスや窒素ガス等の不活性ガス雰囲気下、水素化リチウムアルミニウム−ｔｅｒｔ−ブトキシド等を用いてこれを還元することにより３−ホルミル−２，２，５，５−テトラメチルピロリン−１−オキシルとし、さらにメチルトリホスホニウムブロミド等を用いてこれをビニル化することにより３−ビニル−２，２，５，５−テトラメチルピロリン−１−オキシルを製造することができる。
本発明に係るピロリン系ニトロキシド重合体は、前記ピロリン系ニトロキシド化合物を重合して得られるものである。
前記ピロリン系ニトロキシド化合物を重合する方法としては、特に限定されるものではなく、例えば、塊状重合法および溶液重合法等を用いて重合する方法を挙げることができる。The pyrroline nitroxide polymer according to the present invention is obtained by polymerizing the pyrroline nitroxide compound.
The method for polymerizing the pyrroline nitroxide compound is not particularly limited, and examples thereof include a method of polymerizing using a bulk polymerization method, a solution polymerization method, and the like.
前記塊状重合法を用いて重合する方法としては、例えば、撹拌機、温度計、アルゴンガスや窒素ガス等の不活性ガスを導入するためのガス導入管および冷却管を備えた反応器を用いて、所定量のピロリン系ニトロキシド化合物を仕込み、不活性ガスにより脱酸素した後、撹拌しながら重合開始剤を添加する方法が挙げられる。 Examples of the polymerization method using the bulk polymerization method include using a reactor equipped with a stirrer, a thermometer, a gas introduction pipe for introducing an inert gas such as argon gas or nitrogen gas, and a cooling pipe. There is a method in which a predetermined amount of a pyrroline-based nitroxide compound is charged, deoxygenated with an inert gas, and then a polymerization initiator is added with stirring.
前記溶液重合法を用いて重合する方法としては、例えば、前記塊状重合法を用いて重合する場合において、所定量のピロリン系ニトロキシド化合物とともに不活性溶媒を仕込み、不活性ガスにより脱酸素した後、撹拌しながら重合開始剤を添加する方法が挙げられる。 As a method of polymerizing using the solution polymerization method, for example, in the case of polymerizing using the bulk polymerization method, after adding an inert solvent together with a predetermined amount of pyrroline nitroxide compound, deoxidizing with an inert gas, A method of adding a polymerization initiator while stirring can be mentioned.
前記溶液重合法を用いて重合する場合に使用する不活性溶媒としては、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒；ｎ−ヘキサン、ｎ−ヘプタン、リグロイン等の非環式飽和炭化水素系溶媒；シクロペンタン、メチルシクロペンタン、シクロヘキサン、メチルシクロヘキサン等の環式飽和炭化水素系溶媒；ジエチルエーテル、テトラヒドロフラン等のエーテル系溶媒等の不活性溶媒が挙げられる。これらの中でも、工業的に入手が容易で、安価であり、得られる重合反応生成物の品質が安定する観点から、芳香族炭化水素系溶媒、非環式飽和炭化水素系溶媒およびエーテル系溶媒が好ましく、中でもトルエン、ｎ−ヘキサンおよびテトラヒドロフランが好適に用いられる。 Examples of the inert solvent used for polymerization using the solution polymerization method include aromatic hydrocarbon solvents such as benzene, toluene and xylene; acyclic saturation such as n-hexane, n-heptane and ligroin Hydrocarbon solvents; cyclic saturated hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane; and inert solvents such as ether solvents such as diethyl ether and tetrahydrofuran. Among these, aromatic hydrocarbon solvents, acyclic saturated hydrocarbon solvents and ether solvents are industrially easily available, inexpensive, and stable in quality of the obtained polymerization reaction product. Among these, toluene, n-hexane and tetrahydrofuran are preferably used.
前記溶液重合法を用いて重合する場合における前記不活性溶媒の使用量は、特に制限されるものではないが、反応を円滑に進行させる観点および使用量に見合うだけの効果を得る観点から、ピロリン系ニトロキシド化合物１００重量部に対して１〜２００重量部であることが好ましい。 The amount of the inert solvent used in the polymerization using the solution polymerization method is not particularly limited. However, from the viewpoint of smoothly proceeding the reaction and obtaining an effect that is commensurate with the amount used, pyrroline is used. The amount is preferably 1 to 200 parts by weight based on 100 parts by weight of the nitroxide compound.
前記重合開始剤としては特に限定されず、例えば、アニオン系重合開始剤を用いて重合することができる。アニオン系重合開始剤としては、例えば、シクロペンタジエニルチタニウム（ＩＶ）／メチルアルミノキサン、トリクロロチタニウム（ＩＩＩ）／トリエチルアルミニウム、テトラクロロチタニウム（ＩＶ）／トリエチルアルミニウム、トリクロロバナジウム（ＩＩＩ）／トリエチルアルミニウム、ジクロロコバルト（ＩＩ）／ピリジン／ジエチルアルミニウムクロライド等のチーグラー・ナッタ試薬；ｔｅｒｔ−ブトキシカリウム；ｎ−ブチルマグネシウムブロマイド、イソブチルマグネシウムブロマイド、ｔｅｒｔ−ブチルマグネシウムブロマイド、ｎ−ブチルマグネシウムクロライド、イソブチルマグネシウムクロライド、ｔｅｒｔ−ブチルマグネシウムクロライド等のグリニャール試薬；ｎ−ブチルリチウム、ｔｅｒｔ−ブチルリチウム、１，１−ジフェニルヘキシルリチウム等のアルキルリチウム；ジエチル亜鉛およびジエチル亜鉛／水系開始剤等が挙げられる。これらの中でも、得られる重合反応生成物の品質が安定する観点から、チーグラー・ナッタ試薬が好適に用いられ、特に、シクロペンタジエニルチタニウム（ＩＶ）トリクロリド／メチルアルミノキサン系開始剤が好適に用いられる。 It does not specifically limit as said polymerization initiator, For example, it can superpose | polymerize using an anionic polymerization initiator. Examples of the anionic polymerization initiator include cyclopentadienyl titanium (IV) / methylaluminoxane, trichlorotitanium (III) / triethylaluminum, tetrachlorotitanium (IV) / triethylaluminum, trichlorovanadium (III) / triethylaluminum, Ziegler-Natta reagent such as dichlorocobalt (II) / pyridine / diethylaluminum chloride; tert-butoxy potassium; n-butylmagnesium bromide, isobutylmagnesium bromide, tert-butylmagnesium bromide, n-butylmagnesium chloride, isobutylmagnesium chloride, tert -Grignard reagents such as butylmagnesium chloride; n-butyllithium, tert-butyllithi Arm, alkyl lithium such as 1,1-diphenylhexyllithium diethyl zinc and diethyl zinc / water initiator and the like. Among these, the Ziegler-Natta reagent is preferably used from the viewpoint of stabilizing the quality of the resulting polymerization reaction product, and in particular, the cyclopentadienyl titanium (IV) trichloride / methylaluminoxane initiator is preferably used. .
前記重合開始剤の使用量は、使用する重合開始剤の種類や反応温度により異なるが、通常、ピロリン系ニトロキシド化合物１００重量部に対して０．００００５〜１０重量部であることが好ましい。なお、前記重合反応において、必要に応じてイソプロピルアルコール等の連鎖移動剤やメタノール等の重合停止剤等の添加剤を適宜加えてもよい。 Although the usage-amount of the said polymerization initiator changes with kinds and reaction temperature of a polymerization initiator to be used, it is preferable that it is 0.00005-10 weight part normally with respect to 100 weight part of pyrroline-type nitroxide compounds. In the polymerization reaction, additives such as a chain transfer agent such as isopropyl alcohol and a polymerization terminator such as methanol may be added as necessary.
反応温度としては、使用する重合開始剤の種類により異なるが、通常、−１００〜１００℃が好ましく、−２０〜８０℃がより好ましい。反応時間は前記反応温度により異なるため一概には言えないが、通常、５〜６０時間である。 As reaction temperature, although it changes with kinds of polymerization initiator to be used, -100-100 degreeC is preferable normally and -20-80 degreeC is more preferable. Although the reaction time varies depending on the reaction temperature, it cannot be generally stated, but it is usually 5 to 60 hours.
かくして得られたピロリン系ニトロキシド重合体は、例えば、反応液をヘキサン等の脂肪族炭化水素等の溶媒と混合し、当該重合反応生成物を沈澱させた後、ろ過することにより単離することができる。さらに、メタノール、ヘキサン等を用いて未反応物等を除去、洗浄し、また希塩酸、水等を用いて重合開始剤残渣を除去、洗浄し、乾燥することにより精製することができる。 The pyrroline-based nitroxide polymer thus obtained can be isolated by, for example, mixing the reaction solution with a solvent such as an aliphatic hydrocarbon such as hexane, precipitating the polymerization reaction product, and then filtering. it can. Furthermore, it can be purified by removing and washing unreacted substances using methanol, hexane or the like, and removing, washing and drying the polymerization initiator residue using dilute hydrochloric acid, water or the like.
本発明に係るピロリン系ニトロキシド重合体は、架橋構造を有するものであってもよい。架橋構造を有するピロリン系ニトロキシド重合体は、例えば、前記ピロリン系ニトロキシド化合物を重合する際に架橋剤を添加して、これと共重合させることにより製造することができる。 The pyrroline-based nitroxide polymer according to the present invention may have a crosslinked structure. The pyrroline-based nitroxide polymer having a crosslinked structure can be produced, for example, by adding a crosslinking agent when copolymerizing the pyrroline-based nitroxide compound and copolymerizing it.
前記架橋剤としては、分子内に複数個の重合性不飽和基を有する化合物であれば特に限定されず、例えば、（メタ）アクリル酸系多官能化合物、アリルエーテル系多官能化合物およびビニル系多官能化合物等が挙げられる。（メタ）アクリル酸系多官能化合物としては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、１，３−プロパンジオールジ（メタ）アクリレート、１，３−ブタンジオールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，５−ペンタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，７−ヘプタンジオールジ（メタ）アクリレート、１，８−オクタンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、１，１０−デカンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、グリセリンジ（メタ）アクリレートおよび２−ヒドロキシ−３−（メタ）アクリロイロキシプロピル（メタ）アクリレート等が挙げられる。アリルエーテル系多官能化合物としては、例えば、ジエチレングリコールジアリルエーテルおよびジブチレングリコールジアリルエーテル等が挙げられる。ビニル系多官能化合物としては、例えば、ジビニルベンゼン等が挙げられる。これらの中でも、高い重合反応性を有する観点から、（メタ）アクリル酸系多官能化合物が好適に用いられ、特に、エチレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，８−オクタンジオールジ（メタ）アクリレートおよび１，９−ノナンジオールジ（メタ）アクリレートが好適に用いられる。なお、これら架橋剤は、それぞれ１種単独で用いてもよいし、あるいは２種以上併用してもよい。なお、本明細書において、「（メタ）アクリ」とは、「アクリ」および「メタクリ」を意味する。 The crosslinking agent is not particularly limited as long as it is a compound having a plurality of polymerizable unsaturated groups in the molecule, and examples thereof include (meth) acrylic acid polyfunctional compounds, allyl ether polyfunctional compounds, and vinyl polyfunctional compounds. Examples thereof include functional compounds. Examples of the (meth) acrylic acid polyfunctional compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1 , 3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7 -Heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, glycerin (Meth) acrylate and 2-hydroxy-3- (meth) acryloyloxy propyl (meth) acrylate. Examples of the allyl ether polyfunctional compound include diethylene glycol diallyl ether and dibutylene glycol diallyl ether. Examples of the vinyl polyfunctional compound include divinylbenzene. Among these, from the viewpoint of having high polymerization reactivity, a (meth) acrylic acid polyfunctional compound is preferably used, and in particular, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate are preferably used. In addition, these crosslinking agents may be used individually by 1 type, respectively, or may be used together 2 or more types. In the present specification, “(meth) acryl” means “acryl” and “methacryl”.
前記架橋剤の使用割合は、特に限定されるものではないが、前記ピロリン系ニトロキシド化合物１モルに対して０．００００１〜０．２５モルの割合であることが好ましく、０．００００５〜０．１モルの割合であることがより好ましく、０．０００１〜０．０５モルの割合であることがさらに好ましい。 The ratio of the crosslinking agent used is not particularly limited, but is preferably a ratio of 0.00001 to 0.25 mol with respect to 1 mol of the pyrroline nitroxide compound, and 0.00005 to 0.1. A molar ratio is more preferable, and a 0.0001 to 0.05 molar ratio is even more preferable.
本発明に係るピロリン系ニトロキシド重合体の数平均分子量は５００〜５００００００であることが好ましく、１０００〜１００００００であることがより好ましい。５００未満であると、ピロリン系ニトロキシド重合体が電解液に溶解することになり、当該ピロリン系ニトロキシド重合体を含有する電極活物質を用いた電池の容量が低下するおそれがあり、５００００００を超えると、取り扱いが困難になるおそれがある。なお、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー法によって測定された標準ポリスチレン換算値のことをいう。 The number average molecular weight of the pyrroline-based nitroxide polymer according to the present invention is preferably 500 to 5000000, and more preferably 1000 to 1000000. If it is less than 500, the pyrroline-based nitroxide polymer will be dissolved in the electrolytic solution, and the capacity of the battery using the electrode active material containing the pyrroline-based nitroxide polymer may be reduced. , Handling may be difficult. In addition, the said number average molecular weight means the standard polystyrene conversion value measured by the gel permeation chromatography method.
本発明に係る電極活物質は、本発明に係るピロリン系ニトロキシド重合体を含有するものである。このような電極活物質もまた本発明の１つである。
また、本発明に係る電池は、本発明に係る電極活物質を用いたものである。このような電池もまた本発明の１つである。The electrode active material according to the present invention contains the pyrroline nitroxide polymer according to the present invention. Such an electrode active material is also one aspect of the present invention.
The battery according to the present invention uses the electrode active material according to the present invention. Such a battery is also one aspect of the present invention.
図１に本発明に係る電池の実施形態の一例を示す。図１に示す電池は、正極５と負極３とを、電解質を含有するセパレータ４を介して対向するように重ね合わせ、さらに正極５に正極集電体６を重ね合わせた構成となっている。これらは負極側のステンレス外装１と正極側のステンレス外装１とで外装され、その間には、両者の電気的接触を防ぐ目的で、プラスチック樹脂等の絶縁性材料からなる絶縁パッキン２が配置される。なお、電解質として固体電解質やゲル電解質を用いる場合は、電解質を含有するセパレータ４に代えて、これらの電解質を電極間に介在させる形態にすることもできる。 FIG. 1 shows an example of an embodiment of a battery according to the present invention. The battery shown in FIG. 1 has a configuration in which a positive electrode 5 and a negative electrode 3 are stacked so as to face each other with a separator 4 containing an electrolyte, and a positive electrode current collector 6 is further stacked on the positive electrode 5. These are externally covered with a stainless steel exterior 1 on the negative electrode side and a stainless steel exterior 1 on the positive electrode side, and an insulating packing 2 made of an insulating material such as a plastic resin is disposed between them for the purpose of preventing electrical contact therebetween. . In addition, when using solid electrolyte and gel electrolyte as electrolyte, it can replace with the separator 4 containing electrolyte, and can also be made into the form which interposes these electrolytes between electrodes.
本発明に係る電極活物質は、このような電池において、負極３、正極５または両電極に用いることができる。また、本発明に係る電池は、負極３、正極５または両電極の電極活物質として、本発明に係る電極活物質を用いたものである。
以下に、電池を構成する主な部材等に関して説明する。The electrode active material according to the present invention can be used for the negative electrode 3, the positive electrode 5, or both electrodes in such a battery. In addition, the battery according to the present invention uses the electrode active material according to the present invention as the electrode active material of the negative electrode 3, the positive electrode 5, or both electrodes.
Below, the main members etc. which comprise a battery are demonstrated.
（１）電極活物質
本発明において「電極活物質」とは、充電反応および放電反応等の電極反応に直接寄与する物質のことをいい、電池システムの中心的役割を果たすものである。
本発明に係る電極活物質は、本発明に係るピロリン系ニトロキシド重合体を含有するものであり、正極および／または負極の電極活物質として、本発明に係るピロリン系ニトロキシド重合体をそれぞれ単独で用いてもよいし、また、他の電極活物質と組み合わせて電極活物質としてもよい。(1) Electrode Active Material In the present invention, “electrode active material” refers to a material that directly contributes to electrode reactions such as charge reaction and discharge reaction, and plays a central role in the battery system.
The electrode active material according to the present invention contains the pyrroline nitroxide polymer according to the present invention, and each of the pyrroline nitroxide polymer according to the present invention is used alone as the positive electrode and / or negative electrode active material. Alternatively, the electrode active material may be combined with other electrode active materials.
本発明に係るピロリン系ニトロキシド重合体を正極の電極活物質に用いる場合、他の電極活物質としては、金属酸化物、ジスルフィド化合物、他の安定ラジカル化合物および導電性高分子等を挙げることができる。 When the pyrroline-based nitroxide polymer according to the present invention is used as an electrode active material for a positive electrode, examples of other electrode active materials include metal oxides, disulfide compounds, other stable radical compounds, and conductive polymers. .
前記金属酸化物としては、例えば、ＬｉＭｎＯ２、ＬｉｘＭｎ２Ｏ４（０＜ｘ＜２）等のマンガン酸リチウムまたはスピネル構造を有するマンガン酸リチウム、ＭｎＯ２、ＬｉＣｏＯ２、ＬｉＮｉＯ２、あるいはＬｉｙＶ２Ｏ５（０＜ｙ＜２）、オリビン系材料ＬｉＦｅＰＯ４、スピネル構造中のＭｎの一部を他の遷移金属で置換した材料ＬｉＮｉ０．５Ｍｎ１．５Ｏ４、ＬｉＣｒ０．５Ｍｎ１．５Ｏ４、ＬｉＣｏ０．５Ｍｎ１．５Ｏ４、ＬｉＣｏＭｎＯ４、ＬｉＮｉ０．５Ｍｎ０．５Ｏ２、ＬｉＮｉ０．３３Ｍｎ０．３３Ｃｏ０．３３Ｏ２、ＬｉＮｉ０．８Ｃｏ０．２Ｏ２、ＬｉＮ０．５Ｍｎ１．５−ｚＴｉｚＯ４（０＜ｚ＜１．５）等が挙げられる。Examples of the metal oxide include lithium manganate such as LiMnO 2 and Li x Mn 2 O 4 (0 <x <2), lithium manganate having a spinel structure, MnO 2 , LiCoO 2 , LiNiO 2 , or Li y V 2 O 5 (0 <y <2), olivine-based material LiFePO 4 , materials obtained by substituting a part of Mn in the spinel structure with other transition metals, LiNi 0.5 Mn 1.5 O 4 , LiCr 0. 5 Mn 1.5 O 4 , LiCo 0.5 Mn 1.5 O 4 , LiCoMnO 4 , LiNi 0.5 Mn 0.5 O 2 , LiNi 0.33 Mn 0.33 Co 0.33 O 2 , LiNi 0 0.8 Co 0.2 O 2 , LiN 0.5 Mn 1.5-z Ti z O 4 (0 <z <1.5) and the like.
前記ジスルフィド化合物としては、ジチオグリコール、２，５−ジメルカプト−１，３，４−チアジアゾール、Ｓ−トリアジン−２，４，６−トリチオール等が挙げられる。 Examples of the disulfide compound include dithioglycol, 2,5-dimercapto-1,3,4-thiadiazole, S-triazine-2,4,6-trithiol and the like.
前記他の安定ラジカル化合物としては、ポリ（２，２，６，６−テトラメチルピペリジノキシル−４−イル メタクリレート）等が挙げられる。 Examples of the other stable radical compound include poly (2,2,6,6-tetramethylpiperidinoxyl-4-yl methacrylate).
前記導電性高分子としては、ポリアセチレン、ポリフェニレン、ポリアニリン、ポリピロール等が挙げられる。 Examples of the conductive polymer include polyacetylene, polyphenylene, polyaniline, and polypyrrole.
これらの中では、マンガン酸リチウムおよびＬｉＣｏＯ２が好適に用いられる。これら他の電極活物質は、１種単独を前記ピロリン系ニトロキシド重合体と組み合わせてもよいし、２種以上を組み合わせて使用してもよい。Among these, lithium manganate and LiCoO 2 are preferably used. These other electrode active materials may be used alone or in combination with the pyrroline nitroxide polymer, or may be used in combination of two or more.
前記ピロリン系ニトロキシド重合体を負極の電極活物質に用いる場合、他の電極活物質としては、グラファイトや非晶質カーボン、金属リチウムやリチウム合金、リチウムイオン吸蔵炭素、金属ナトリウム、他の安定ラジカル化合物および導電性高分子等を挙げることができる。 When the pyrroline-based nitroxide polymer is used as an electrode active material for a negative electrode, other electrode active materials include graphite, amorphous carbon, metallic lithium and lithium alloy, lithium ion storage carbon, metallic sodium, and other stable radical compounds. And conductive polymers.
他の安定ラジカル化合物としては、ポリ（２，２，６，６−テトラメチルピペリジノキシル−４−イル メタクリレート）等が挙げられる。 Other stable radical compounds include poly (2,2,6,6-tetramethylpiperidinoxyl-4-yl methacrylate) and the like.
これらの中でも特に、金属リチウムまたはグラファイトと組み合わせることが好ましい。なお、これらの形状としては特に限定されず、薄膜状のもの、バルク状のもの、粉末を固めたもの、繊維状のもの、フレーク状のもの等であってもよい。これら他の電極活物質は、１種単独を前記ピロリン系ニトロキシド重合体と組み合わせてもよいし、２種以上を組み合わせて使用してもよい。 Among these, it is preferable to combine with metallic lithium or graphite. These shapes are not particularly limited, and may be a thin film, a bulk, a powder, a fiber, a flake, or the like. These other electrode active materials may be used alone or in combination with the pyrroline nitroxide polymer, or may be used in combination of two or more.
本発明に係る電池は、正極もしくは負極の一方の電極、または両方の電極における電極活物質として、本発明に係るピロリン系ニトロキシド重合体を含有する電極活物質を用いるが、一方の電極にのみ前記ピロリン系ニトロキシド重合体を含有する電極活物質を用いる場合、もう一方の電極における電極活物質としては、前記他の電極活物質として例示した従来公知の電極活物質を用いることができる。 The battery according to the present invention uses the electrode active material containing the pyrroline-based nitroxide polymer according to the present invention as the electrode active material of one of the positive electrode or the negative electrode, or both electrodes, but only for one electrode. When an electrode active material containing a pyrroline-based nitroxide polymer is used, a conventionally known electrode active material exemplified as the other electrode active material can be used as the electrode active material in the other electrode.
本発明において、エネルギー密度の観点から、前記ピロリン系ニトロキシド重合体を含有する電極活物質は、正極の電極活物質として用いるのが好ましく、ピロリン系ニトロキシド重合体を前記他の電極活物質と組み合わせることなく単独で用いるのがより好ましい。また、このときの負極の電極活物質としては、金属リチウムまたはグラファイトを用いることが好ましい。 In the present invention, from the viewpoint of energy density, the electrode active material containing the pyrroline-based nitroxide polymer is preferably used as a positive electrode active material, and the pyrroline-based nitroxide polymer is combined with the other electrode active material. It is more preferable to use it alone. Moreover, it is preferable to use metallic lithium or graphite as the electrode active material of the negative electrode at this time.
（２）導電付与剤（補助導電材）およびイオン伝導補助材
本発明に係る電極活物質を正極の電極活物質として使用する場合、インピーダンスを低下させ、エネルギー密度、出力特性を向上させる目的で、導電付与剤（補助導電材）やイオン伝導補助材を混合させてもよい。(2) Conductivity-imparting agent (auxiliary conductive material) and ion conduction auxiliary material When the electrode active material according to the present invention is used as an electrode active material for a positive electrode, for the purpose of reducing impedance and improving energy density and output characteristics, A conductivity-imparting agent (auxiliary conductive material) or an ion conduction auxiliary material may be mixed.
前記補助導電材としては、グラファイト、カーボンブラック、アセチレンブラック等の炭素質微粒子、気相成長炭素繊維（ＶＧＣＦ）、カーボンナノチューブ等の炭素繊維、ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン、ポリアセン等の導電性高分子が挙げられる。
また、前記イオン伝導補助材としては、高分子ゲル電解質、高分子固体電解質等が挙げられる。これらの中でも、炭素繊維が好適に用いられ、中でも気相成長炭素繊維がより好適に用いられる。炭素繊維を用いることにより、電極の引張り強度がより大きくなり、電極にひびが入ったり剥がれたりすることが少なくなる。これら補助導電材やイオン伝導補助材は、１種単独で用いてもよいし、あるいは２種以上を併用してもよい。
前記補助導電材やイオン伝導補助材を用いる場合、電極中における混合割合としては、１０〜８０重量％が好ましい。Examples of the auxiliary conductive material include carbonaceous fine particles such as graphite, carbon black, and acetylene black, carbon fibers such as vapor grown carbon fiber (VGCF) and carbon nanotubes, polyaniline, polypyrrole, polythiophene, polyacetylene, and polyacene. Molecule.
Examples of the ion conduction auxiliary material include polymer gel electrolytes and polymer solid electrolytes. Among these, carbon fibers are preferably used, and vapor-grown carbon fibers are more preferably used. By using carbon fiber, the tensile strength of the electrode is increased, and the electrode is less likely to crack or peel off. These auxiliary conductive materials and ion conductive auxiliary materials may be used alone or in combination of two or more.
When the auxiliary conductive material or the ion conductive auxiliary material is used, the mixing ratio in the electrode is preferably 10 to 80% by weight.
（３）結着剤
本発明に係る前記電極活物質では、各構成材料間の結びつきを強めるために、結着剤を混合させてもよい。
前記結着剤としては、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、ビニリデンフロライド−ヘキサフルオロプロピレン共重合体、ビニリデンフロライド−テトラフルオロエチレン共重合体、スチレン−ブタジエン共重合ゴム、ポリプロピレン、ポリエチレン、ポリイミド、各種ポリウレタン等の樹脂バインダーが挙げられる。これら結着剤は、１種単独で用いてもよいし、あるいは２種以上を併用してもよい。
前記結着剤を用いる場合、電極中の混合割合としては、５〜３０重量％が好ましい。(3) Binder In the electrode active material according to the present invention, a binder may be mixed in order to strengthen the connection between the constituent materials.
Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, polypropylene, polyethylene, and polyimide. And resin binders such as various polyurethanes. These binders may be used individually by 1 type, or may use 2 or more types together.
When the binder is used, the mixing ratio in the electrode is preferably 5 to 30% by weight.
（４）増粘剤
本発明に係る電極活物質を形成させるためのスラリーを作製しやすくするために、増粘剤を混合させてもよい。
前記増粘剤としては、カルボキシメチルセルロース、ポリエチレンオキシド、ポリプロピレンオキシド、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルヒドロキシエチルセルロース、ポリビニルアルコール、ポリアクリルアミド、ポリアクリル酸ヒドロキシエチル、ポリアクリル酸アンモニウム、ポリアクリル酸ソーダ等が挙げられる。これら増粘剤は、１種単独で用いてもよいし、あるいは２種以上を併用してもよい。
前記増粘剤を用いる場合、電極中の混合割合としては、０．１〜５重量％が好ましい。(4) Thickener In order to make it easy to produce a slurry for forming the electrode active material according to the present invention, a thickener may be mixed.
Examples of the thickener include carboxymethyl cellulose, polyethylene oxide, polypropylene oxide, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl hydroxyethyl cellulose, polyvinyl alcohol, polyacrylamide, polyethyl acrylate, ammonium polyacrylate, and sodium polyacrylate. Is mentioned. These thickeners may be used individually by 1 type, or may use 2 or more types together.
When the thickener is used, the mixing ratio in the electrode is preferably 0.1 to 5% by weight.
（５）触媒
本発明に係る前記電極活物質において、電極反応をより円滑に行うために、酸化還元反応を助ける触媒を混合させてもよい。
前記触媒としては、ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン、ポリアセン等の導電性高分子、ピリジン誘導体、ピロリドン誘導体、ベンズイミダゾール誘導体、ベンゾチアゾール誘導体、アクリジン誘導体等の塩基性化合物、金属イオン錯体等が挙げられる。これら触媒は、１種単独で用いてもよいし、あるいは２種以上を併用してもよい。
前記触媒を用いる場合、電極中の混合割合としては、１０重量％以下が好ましい。(5) Catalyst In the said electrode active material which concerns on this invention, in order to perform an electrode reaction more smoothly, you may mix the catalyst which assists an oxidation-reduction reaction.
Examples of the catalyst include conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyacene, basic compounds such as pyridine derivatives, pyrrolidone derivatives, benzimidazole derivatives, benzothiazole derivatives, and acridine derivatives, and metal ion complexes. . These catalysts may be used individually by 1 type, or may use 2 or more types together.
When the catalyst is used, the mixing ratio in the electrode is preferably 10% by weight or less.
（６）集電体およびセパレータ
本発明に係る電極活物質に接触させて用いられる集電体としては、ニッケル、アルミニウム、銅、金、銀、アルミニウム合金、ステンレス、炭素等が挙げられ、箔、金属平板、メッシュ状等の形状のものを用いることができる。また、集電体に触媒効果を持たせたり、電極活物質と集電体とを化学結合させたりしてもよい。
一方、セパレータとしては、ポリエチレン、ポリプロピレン等からなる多孔質フィルムや不織布等を挙げることができる。(6) Current collector and separator Examples of the current collector used in contact with the electrode active material according to the present invention include nickel, aluminum, copper, gold, silver, aluminum alloy, stainless steel, carbon, foil, A metal flat plate or mesh shape can be used. Further, the current collector may have a catalytic effect, or the electrode active material and the current collector may be chemically bonded.
On the other hand, examples of the separator include porous films and nonwoven fabrics made of polyethylene, polypropylene, and the like.
（７）電解質
本発明に係る電池において、電解質は、負極と正極の両極間の荷電担体輸送を行うものであり、一般には２０℃で１０−５〜１０−１Ｓ／ｃｍのイオン伝導性を有していることが好ましい。前記電解質としては、例えば、電解質塩を溶媒に溶解した電解液を用いることができる。
前記電解質塩としては、例えば、ＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ、Ｌｉ（Ｃ２Ｆ５ＳＯ２）２Ｎ、Ｌｉ（ＣＦ３ＳＯ２）３Ｃ、Ｌｉ（Ｃ２Ｆ５ＳＯ２）３Ｃ等の従来公知の材料を挙げることができる。これら電解質塩は、１種単独で用いてもよいし、あるいは２種以上を併用してもよい。
前記溶媒としては、例えば、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、γ−ブチロラクトン、テトラヒドロフラン、ジオキソラン、スルホラン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン等の有機溶媒を挙げることができる。これら溶媒は、１種単独で用いてもよいし、あるいは２種以上を併用してもよい。(7) Electrolyte In the battery according to the present invention, the electrolyte performs charge carrier transport between the negative electrode and the positive electrode, and generally has an ionic conductivity of 10 −5 to 10 −1 S / cm at 20 ° C. It is preferable to have. As the electrolyte, for example, an electrolytic solution in which an electrolyte salt is dissolved in a solvent can be used.
Examples of the electrolyte salt include LiPF 6 , LiClO 4 , LiBF 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) 2 N, Li (CF 3 SO 2 ) Conventionally known materials such as 3 C and Li (C 2 F 5 SO 2 ) 3 C can be mentioned. These electrolyte salts may be used individually by 1 type, or may use 2 or more types together.
Examples of the solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxolane, sulfolane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl. An organic solvent such as -2-pyrrolidone can be mentioned. These solvents may be used alone or in combination of two or more.
また、前記電解質として高分子化合物に前記電解質塩を含有させた固体電解質や高分子化合物に前記電解液を含ませてゲル状にした固体電解質を用いることもできる。
前記高分子化合物としては、ポリフッ化ビニリデン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、フッ化ビニリデン−エチレン共重合体、フッ化ビニリデン−モノフルオロエチレン共重合体、フッ化ビニリデン−トリフルオロエチレン共重合体、フッ化ビニリデン−テトラフルオロエチレン共重合体、フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン三元共重合体等のフッ化ビニリデン系重合体；アクリロニトリル−メチルメタクリレート共重合体、アクリロニトリル−メチルアクリレート共重合体、アクリロニトリル−エチルメタクリレート共重合体、アクリロニトリル−エチルアクリレート共重合体、アクリロニトリル−メタクリル酸共重合体、アクリロニトリル−アクリル酸共重合体、アクリロニトリル−ビニルアセテート共重合体等のアクリロニトリル系重合体；さらにポリエチレンオキサイド、エチレンオキサイド−プロピレンオキサイド共重合体、これらのアクリレート体やメタクリレート体の重合体等が挙げられる。Further, as the electrolyte, a solid electrolyte in which the electrolyte salt is contained in a polymer compound or a solid electrolyte in which the electrolyte solution is contained in a polymer compound to form a gel can be used.
Examples of the polymer compound include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-ethylene copolymer, vinylidene fluoride-monofluoroethylene copolymer, and vinylidene fluoride-trifluoroethylene copolymer. Polymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-based polymer such as vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer; acrylonitrile-methyl methacrylate copolymer, acrylonitrile-methyl Acrylate copolymer, acrylonitrile-ethyl methacrylate copolymer, acrylonitrile-ethyl acrylate copolymer, acrylonitrile-methacrylic acid copolymer, acrylonitrile-acrylic acid copolymer, acryloni Lil - acrylonitrile polymers such as vinyl acetate copolymer; and polyethylene oxide, ethylene oxide - propylene oxide copolymer, polymer and the like of these acrylates body or methacrylate products thereof.
（８）電池形状
本発明に係る電池の形状は特に限定されず、従来公知のものを用いることができる。例えば、電極積層体、あるいは巻回体を金属ケース、樹脂ケース、あるいはアルミニウム箔等の金属箔と合成樹脂フィルムからなるラミネートフィルム等によって封止したもの等が挙げられ、円筒型、角型、コイン型、およびシート型等が挙げられる。(8) Battery shape The shape of the battery according to the present invention is not particularly limited, and conventionally known batteries can be used. For example, an electrode laminate or a wound body is sealed with a metal case, a resin case, or a laminate film composed of a metal foil such as an aluminum foil and a synthetic resin film, etc. Examples include molds and sheet molds.
（９）電池の製造方法
本発明に係る電池の製造方法としては特に限定されず、材料に応じて適宜選択した方法を用いることができる。例えば、本発明に係る電極活物質、導電付与剤等に溶媒を加えスラリー状にして電極集電体に塗布し、加熱もしくは常温で溶媒を揮発させることにより電極を作製し、さらにこの電極を対極、セパレータを挟んで積層または巻回して外装体で包み、電解液を注入して封止するといった方法である。スラリー化のための溶媒としては、テトラヒドロフラン、ジエチルエーテル、エチレングリコールジメチルエーテル、ジオキサン等のエーテル系溶媒；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン等のアミン系溶媒；ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒；ヘキサン、ヘプタン等の脂肪族炭化水素系溶媒；クロロホルム、ジクロロメタン、ジクロロエタン、トリクロロエタン、四塩化炭素等のハロゲン化炭化水素系溶媒；アセトン、メチルエチルケトン等のアルキルケトン系溶媒；メタノール、エタノール、イソプロピルアルコール等のアルコール系溶媒；ジメチルスルホキシド、水等が挙げられる。また、電極の作製法としては、電極活物質、導電付与剤等を乾式で混練した後、薄膜化し電極集電体上に積層する方法もある。(9) Battery Manufacturing Method The battery manufacturing method according to the present invention is not particularly limited, and a method appropriately selected according to the material can be used. For example, a solvent is added to the electrode active material, the conductivity-imparting agent, etc. according to the present invention to form a slurry, which is applied to the electrode current collector, and the electrode is produced by heating or volatilizing the solvent at room temperature. In this method, the separators are stacked or wound, wrapped with an outer package, and injected with an electrolyte solution to be sealed. Solvents for slurrying include ether solvents such as tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether and dioxane; amine solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; benzene, toluene and xylene Aromatic hydrocarbon solvents such as hexane, heptane, etc .; Halogenated hydrocarbon solvents such as chloroform, dichloromethane, dichloroethane, trichloroethane, carbon tetrachloride; Alkyl ketone solvents such as acetone and methyl ethyl ketone Alcoholic solvents such as methanol, ethanol and isopropyl alcohol; dimethyl sulfoxide, water and the like. In addition, as an electrode manufacturing method, there is a method in which an electrode active material, a conductivity-imparting agent, and the like are kneaded in a dry manner and then thinned and laminated on an electrode current collector.
本発明に係る電池の製造方法では、電極活物質を構成する化合物として前記ピロリン系ニトロキシド重合体そのものを用いる場合と、電極反応によって前記ピロリン系ニトロキシド重合体に変化する重合体を用いる場合とがある。このような電極反応によって前記ピロリン系ニトロキシド重合体に変化する重合体の例としては、前記ピロリン系ニトロキシド重合体を還元したアニオン体と、リチウムイオンやナトリウムイオンといった電解質カチオンとからなるリチウム塩やナトリウム塩、および、前記ピロリン系ニトロキシド重合体を酸化したカチオン体と、ＰＦ６ −やＢＦ４ −といった電解質アニオンとからなる塩等が挙げられる。
本発明に係る電池において、電極からのリードの取り出し、外装等のその他の製造条件は電池の製造方法として従来公知の方法を用いることができる。In the battery manufacturing method according to the present invention, the pyrroline nitroxide polymer itself may be used as a compound constituting the electrode active material, or a polymer that changes to the pyrroline nitroxide polymer by an electrode reaction may be used. . Examples of the polymer that changes to the pyrroline nitroxide polymer by such an electrode reaction include a lithium salt or sodium consisting of an anion obtained by reducing the pyrroline nitroxide polymer and an electrolyte cation such as lithium ion or sodium ion. salt, and a cation body oxidizing the pyrophosphate-based nitroxide polymer, PF 6 - and BF 4 - salts, and the like made of an electrolyte anions such.
In the battery according to the present invention, a conventionally known method can be used as the battery manufacturing method for other manufacturing conditions such as lead extraction from the electrode and outer packaging.
本発明によると、大きな電流を取り出すことができ、かつ繰り返し充放電を行っても容量の低下が少ない電池の電極材料として用いられるピロリン系ニトロキシド重合体、当該重合体を含有する電極活物質および当該電極活物質を用いた電池を提供することができる。 According to the present invention, a pyrroline-based nitroxide polymer that can be used as an electrode material for a battery that can take out a large current and has little decrease in capacity even after repeated charge and discharge, an electrode active material containing the polymer, and the A battery using an electrode active material can be provided.
以下に、製造例、実施例により、本発明を具体的に説明するが、本発明はこれら製造例、実施例によってなんら限定されるものではない。 The present invention will be specifically described below with reference to production examples and examples, but the present invention is not limited to these production examples and examples.
［製造例１］（ピロリン系ニトロキシド化合物の製造）
撹拌機、温度計、還流冷却管および流量計を備えた１００ｍＬ容の４つ口フラスコに、３−カルバモイル−２，２，５，５−テトラメチルピロリン−１−オキシル１．１７ｇおよび１０ｗｔ％水酸化ナトリウム水溶液１６．８ｍＬを仕込み、懸濁させ、１００℃にて２時間保持した。その後、適量の希塩酸を加えて中和し、黄色溶液を得た。これにジエチルエーテル５０ｍＬを加えて抽出した後、濃縮することにより、黄色結晶の３−カルボキシ−２，２，５，５−テトラメチルピロリン−１−オキシル１．１２ｇを得た。[Production Example 1] (Production of pyrroline nitroxide compound)
To a 100 mL four-necked flask equipped with a stirrer, thermometer, reflux condenser and flow meter, 1.17 g of 3-carbamoyl-2,2,5,5-tetramethylpyrrolin-1-oxyl and 10 wt% water 16.8 mL of an aqueous sodium oxide solution was charged, suspended, and held at 100 ° C. for 2 hours. Thereafter, an appropriate amount of dilute hydrochloric acid was added for neutralization to obtain a yellow solution. This was extracted with 50 mL of diethyl ether, and concentrated to obtain 1.12 g of 3-carboxy-2,2,5,5-tetramethylpyrroline-1-oxyl as yellow crystals.
得られた３−カルボキシ−２，２，５，５−テトラメチルピロリン−１−オキシルは、下記の物性を有することから同定することができた。
ＩＲ（ＫＢｒ）：３３００，２５００，１７０７ｃｍ−１
分子量（大気圧イオン化法による質量分析）：１８４The obtained 3-carboxy-2,2,5,5-tetramethylpyrroline-1-oxyl could be identified from the following physical properties.
IR (KBr): 3300, 2500, 1707 cm −1
Molecular weight (mass spectrometry by atmospheric pressure ionization method): 184
得られた３−カルボキシ−２，２，５，５−テトラメチルピロリン−１−オキシル１ｇを、撹拌機、アルゴンガス導入管および温度計を備え、あらかじめアルゴンガスで置換した１００ｍＬ容の４つ口フラスコに仕込み、ベンゼン１２ｍＬ／ピリジン０．４４ｍＬの混合溶媒を加えて溶解させた。次に、アルゴン雰囲気下、５℃に冷却し、塩化チオニル０．４４ｍＬ／ベンゼン２ｍＬを加え、１時間撹拌した後、溶媒を留去し、ＴＨＦ１０ｍＬを加えて溶解させた。その後、−７８℃に冷却し、同温度で１ｍｏｌ／Ｌ水素化リチウムアルミニウム−ｔｅｒｔ−ブトキシドＴＨＦ溶液５．４ｍＬを２時間かけて滴下した。次いで、酢酸エチル５０ｍＬを用いて抽出した後、濃縮することにより、黄色結晶の３−ホルミル−２，２，５，５−テトラメチルピロリン−１−オキシル０．４４ｇを得た。 4 mL of 100 mL capacity obtained by replacing 1 g of the obtained 3-carboxy-2,2,5,5-tetramethylpyrrolin-1-oxyl with a stirrer, an argon gas introduction tube and a thermometer and previously substituted with argon gas The flask was charged and dissolved by adding a mixed solvent of 12 mL of benzene / 0.44 mL of pyridine. Next, it was cooled to 5 ° C. in an argon atmosphere, 0.44 mL of thionyl chloride / 2 mL of benzene was added and stirred for 1 hour, and then the solvent was distilled off, and 10 mL of THF was added and dissolved. Thereafter, the mixture was cooled to −78 ° C., and 5.4 mL of a 1 mol / L lithium aluminum hydride-tert-butoxide THF solution was added dropwise at the same temperature over 2 hours. Subsequently, extraction was performed using 50 mL of ethyl acetate, followed by concentration to obtain 0.44 g of 3-formyl-2,2,5,5-tetramethylpyrroline-1-oxyl as yellow crystals.
得られた３−ホルミル−２，２，５，５−テトラメチルピロリン−１−オキシルは、下記の物性を有することから同定することができた。
ＩＲ（ＫＢｒ）：２８３４，２７３６，１６８８ｃｍ−１
分子量（大気圧イオン化法による質量分析）：１６８The obtained 3-formyl-2,2,5,5-tetramethylpyrroline-1-oxyl could be identified from the following physical properties.
IR (KBr): 2834, 2736, 1688 cm −1
Molecular weight (mass spectrometry by atmospheric pressure ionization method): 168
次に、撹拌機、アルゴンガス導入管および温度計を備え、あらかじめアルゴンガスで置換した１００ｍＬ容の４つ口フラスコに、０℃にて、メチルトリホスホニウムブロミド３．１９ｇ、炭酸カリウム１．３６ｇ、テトラヒドロフラン８．４ｍＬを仕込み、溶解させ、３０分間保持した。その後、３−ホルミル−２，２，５，５−テトラメチルピロリン−１−オキシル０．５０ｇ／テトラヒドロフラン２．３ｍＬを加え、２５℃にて４８時間攪拌した後、ジエチルエーテル５０ｍＬを加えて抽出した後、濃縮することにより、橙色油状の前記一般式（１）で表されるピロリン系ニトロキシド化合物である３−ビニル−２，２，５，５−テトラメチルピロリン−１−オキシル０．２３ｇを得た。 Next, in a 100 mL four-neck flask equipped with a stirrer, an argon gas introduction tube and a thermometer and previously substituted with argon gas, at 0 ° C., 3.19 g of methyltriphosphonium bromide, 1.36 g of potassium carbonate, 8.4 mL of tetrahydrofuran was charged, dissolved, and held for 30 minutes. Thereafter, 0.50 g of 3-formyl-2,2,5,5-tetramethylpyrroline-1-oxyl / 2.3 mL of tetrahydrofuran was added, and the mixture was stirred at 25 ° C. for 48 hours, followed by extraction with 50 mL of diethyl ether. Thereafter, by concentration, 0.23 g of 3-vinyl-2,2,5,5-tetramethylpyrrolin-1-oxyl, which is a pyrroline-based nitroxide compound represented by the above general formula (1) as an orange oil, is obtained. It was.
得られたピロリン系ニトロキシド化合物は、下記の物性を有することから同定することができた。なお、ＮＭＲは、フェニルヒドラジンでラジカル部位を還元することにより測定した。
１Ｈ ＮＭＲ（ＣＤＣｌ３）：６．１６，５．６０，５．４１，５．１１，１．３９，１．２５ｐｐｍ
１３Ｃ ＮＭＲ（ＣＤＣｌ３）：１３１．３，１３０．２，１１５．１，１１３．７，６９．８，６７．３，２５．３，２４．６ｐｐｍ
ＩＲ（ＫＢｒ）：２９７４，１６３５，１５９３ｃｍ−１
分子量（大気圧イオン化法による質量分析）：１６６The obtained pyrroline-based nitroxide compound could be identified from the following physical properties. NMR was measured by reducing the radical site with phenylhydrazine.
1 H NMR (CDCl 3 ): 6.16, 5.60, 5.41, 5.11, 1.39, 1.25 ppm
13 C NMR (CDCl 3 ): 131.3, 130.2, 115.1, 113.7, 69.8, 67.3, 25.3, 24.6 ppm
IR (KBr): 2974, 1635, 1593 cm −1
Molecular weight (mass spectrometry by atmospheric pressure ionization method): 166
［製造例２］
攪拌機、窒素ガス導入管、温度計、還流冷却管を備えた５００ｍＬ容の４つ口フラスコに、２，２，６，６−テトラメチル−４−ピペリジニルメタクリレート７０．０ｇ（３１１ミリモル）およびテトラヒドロフラン１５０ｍＬを仕込み、均一溶液を得た。この溶液を２５℃に保ちながら、窒素ガスを通じて反応系内の酸素を除去した後、重合開始剤としてα、α’−アゾビスイソブチロニトリル０．３５８ｇ（２．２ミリモル）を加えて、攪拌下、５０℃にて６時間反応させた。反応終了後、反応液を室温まで冷却し、ヘキサン２０００ｍＬ中に加えた後、ろ過してポリメタクリル酸イミノ化合物を得た。得られたポリメタクリル酸イミノ化合物をヘキサン５００ｍＬで洗浄した後、減圧乾燥して白色粉体のポリメタクリル酸イミノ化合物６９．５ｇを得た。
次に、得られたポリメタクリル酸イミノ化合物１８ｇおよびクロロホルム１８０ｇを攪拌機、温度計、還流冷却管および滴下ロートを備えた５００ｍＬ容の４つ口フラスコに仕込んで溶解させた。そこへ、２５℃で、タングステン酸ナトリウム２水和物０．２４ｇを溶解させた６０重量％過酸化水素水１２０ｇを５時間かけて滴下した。滴下終了後反応を１０時間継続した。反応後１時間静置して有機相を分離し、クロロホルム相を留去した。残った固形分を粉砕し、得られた粉末を減圧乾燥させてポリメタクリル酸ニトロキシド化合物１５．７ｇを得た。[Production Example 2]
In a 500 mL four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube, 70.0 g (311 mmol) of 2,2,6,6-tetramethyl-4-piperidinyl methacrylate and 150 mL of tetrahydrofuran was charged to obtain a uniform solution. While maintaining this solution at 25 ° C., oxygen in the reaction system was removed through nitrogen gas, and then α, α′-azobisisobutyronitrile 0.358 g (2.2 mmol) was added as a polymerization initiator, The mixture was reacted at 50 ° C. for 6 hours under stirring. After completion of the reaction, the reaction solution was cooled to room temperature, added to 2000 mL of hexane, and then filtered to obtain a polymethacrylic acid imino compound. The obtained polymethacrylic acid imino compound was washed with 500 mL of hexane and then dried under reduced pressure to obtain 69.5 g of a white powdery polymethacrylic acid imino compound.
Next, 18 g of the resulting polymethacrylic acid imino compound and 180 g of chloroform were charged and dissolved in a 500 mL four-necked flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel. Thereto, 120 g of 60 wt% hydrogen peroxide solution in which 0.24 g of sodium tungstate dihydrate was dissolved was dropped at 25 ° C. over 5 hours. The reaction was continued for 10 hours after completion of the dropwise addition. The reaction was allowed to stand for 1 hour to separate the organic phase, and the chloroform phase was distilled off. The remaining solid was pulverized, and the resulting powder was dried under reduced pressure to obtain 15.7 g of a polymethacrylic acid nitroxide compound.
［実施例１］（ピロリン系ニトロキシド重合体の製造）
撹拌機およびアルゴンガス導入管を備えた５ｍＬ容のナス型フラスコに、製造例１と同様にして得られたピロリン系ニトロキシド化合物０．１７ｇ（１ミリモル）を仕込み、２５℃に保ちながら、アルゴンガスを通じて反応系内の酸素を除去した。次に、重合開始剤としてのシクロペンタジエニルチタニウム（ＩＶ）トリクロリド０．１３ｍｇ（０．０００６ミリモル）、メチルアルミノキサン１１．２５ｍｇ（０．１９４ミリモル）を加えて、アルゴンガス雰囲気下、２５℃で撹拌下２２時間重合反応させた後、適量のメタノールを添加して反応を停止させた。反応終了後、ヘキサン５０ｍＬ中に加え、ろ過した後、ヘキサン１０ｍＬで洗浄し、減圧乾燥することにより薄茶色のピロリン系ニトロキシド重合体０．０２ｇを得た（収率１１％）。
得られたピロリン系ニトロキシド重合体について、数平均分子量を測定したところ、２６０００であった。なお、数平均分子量は、ゲルパーミエーションクロマトグラフィー（株式会社島津製作所製）を用いて、ＬｉＣｌ（０．０１ｍｏｌ／Ｌ）、Ｈ３ＰＯ４（０．０２ｍｏｌ／Ｌ）を含むＮ，Ｎ−ジメチルホルムアミド中３０℃にて測定し、標準ポリスチレンを基準にして算出した。[Example 1] (Production of pyrroline nitroxide polymer)
Into a 5 mL eggplant-shaped flask equipped with a stirrer and an argon gas introduction tube was charged 0.17 g (1 mmol) of the pyrroline nitroxide compound obtained in the same manner as in Production Example 1, and the argon gas was maintained at 25 ° C. To remove oxygen in the reaction system. Next, 0.13 mg (0.0006 mmol) of cyclopentadienyltitanium (IV) trichloride as a polymerization initiator and 11.25 mg (0.194 mmol) of methylaluminoxane were added, and the reaction was performed at 25 ° C. under an argon gas atmosphere. After the polymerization reaction for 22 hours under stirring, an appropriate amount of methanol was added to stop the reaction. After completion of the reaction, the mixture was added to 50 mL of hexane, filtered, washed with 10 mL of hexane, and dried under reduced pressure to obtain 0.02 g of a light brown pyrroline nitroxide polymer (yield 11%).
It was 26000 when the number average molecular weight was measured about the obtained pyrroline nitroxide polymer. The number average molecular weight is N, N-dimethyl containing LiCl (0.01 mol / L) and H 3 PO 4 (0.02 mol / L) using gel permeation chromatography (manufactured by Shimadzu Corporation). It was measured at 30 ° C. in formamide and calculated based on standard polystyrene.
［実施例２］（ピロリン系ニトロキシド重合体の製造）
重合温度を５０℃とする以外は、実施例１と同様にして、薄茶色のピロリン系ニトロキシド０．０３ｇを得た（収率１７％）。
得られたピロリン系ニトロキシド重合体について、数平均分子量を測定したところ、２１０００であった。なお、数平均分子量は、ゲルパーミエーションクロマトグラフィー（株式会社島津製作所製）を用いて、ＬｉＣｌ（０．０１ｍｏｌ／Ｌ）、Ｈ３ＰＯ４（０．０２ｍｏｌ／Ｌ）を含むＮ，Ｎ−ジメチルホルムアミド中３０℃にて測定し、標準ポリスチレンを基準にして算出した。[Example 2] (Production of pyrroline nitroxide polymer)
Except for setting the polymerization temperature to 50 ° C., 0.03 g of light brown pyrroline nitroxide was obtained in the same manner as in Example 1 (yield 17%).
The number average molecular weight of the obtained pyrroline nitroxide polymer was measured and found to be 21,000. The number average molecular weight is N, N-dimethyl containing LiCl (0.01 mol / L) and H 3 PO 4 (0.02 mol / L) using gel permeation chromatography (manufactured by Shimadzu Corporation). It was measured at 30 ° C. in formamide and calculated based on standard polystyrene.
［実施例３］（ピロリン系ニトロキシド重合体を含有する電極の酸化還元特性）
実施例１で得られたピロリン系ニトロキシド重合体０．０１ｇ、補助導電材として気相成長炭素繊維０．０８ｇおよび結着剤としてのポリフッ化ビニリデン０．０１ｇをそれぞれ量りとり、Ｎ−メチルピロリドンを添加し、メノウ乳鉢を用いて混練した。１０分ほど湿式混合して得られたスラリー状の混合体をＩＴＯ基板上に塗布し、真空中６０℃で一晩乾燥した。
この電極について、対極に白金コイル、参照極にＡｇ／ＡｇＣｌ、電解液として０．５Ｍ（Ｃ４Ｈ９）４ＮＣｌＯ４アセトニトリル溶液を用いて、電位掃引範囲０．５−１．０Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ）でのサイクリックボルタモグラムを測定したところ、０．７５Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ）にニトロキシドラジカルのｐ型レドックス由来の酸化還元波が現れ、繰り返し掃引しても酸化還元波は安定していた。[Example 3] (Redox characteristics of electrode containing pyrroline-based nitroxide polymer)
0.01 g of the pyrroline nitroxide polymer obtained in Example 1, 0.08 g of vapor-grown carbon fiber as an auxiliary conductive material, and 0.01 g of polyvinylidene fluoride as a binder were weighed, and N-methylpyrrolidone was added. It was added and kneaded using an agate mortar. A slurry-like mixture obtained by wet mixing for about 10 minutes was applied onto an ITO substrate and dried overnight at 60 ° C. in a vacuum.
For this electrode, a platinum coil was used for the counter electrode, Ag / AgCl was used for the reference electrode, and a 0.5 M (C 4 H 9 ) 4 NClO 4 acetonitrile solution was used as the electrolyte, and a potential sweep range of 0.5 to 1.0 V (vs. When the cyclic voltammogram at Ag / AgCl) was measured, a redox wave derived from the p-type redox of the nitroxide radical appeared at 0.75 V (vs. Ag / AgCl), and the redox wave was stable even after repeated sweeps. It was.
［実施例４］（ピロリン系ニトロキシド重合体を含有する電極活物質を用いた電池）
実施例１で得られたピロリン系ニトロキシド重合体０．０１ｇ、補助導電材として気相成長炭素繊維０．０８ｇおよび結着剤としてのポリフッ化ビニリデン０．０１ｇをそれぞれ量りとり、Ｎ−メチルピロリドンを添加し、メノウ乳鉢を用いて混練した。１０分ほど湿式混合して得られたスラリー状の混合体をアルミ箔上に塗布し延伸した後、真空中６０℃で一晩乾燥した。その後、直径１２ｍｍの円形に打ち抜き、コイン電極を成型した。なお、この電極の質量は１３．０ｍｇであった。
次に、得られた電極を電解液に浸して、電極中の空隙に電解液を染み込ませた。電解液としては、１．０ｍｏｌ／ＬのＬｉＰＦ６電解質塩を含むエチレンカーボネート／ジエチルカーボネート混合溶液（混合体積比１：１）を用いた。電解液を含浸させた電極は、正極集電体を兼ねたステンレス外装（宝泉株式会社製）上に置き、その上に同じく電解液を含浸させたポリプロピレン多孔質フィルムセパレータを積層した。さらに負極となるリチウムディスクを積層し、周囲に絶縁パッキンを配置した状態で負極側ステンレス外装（宝泉株式会社製）を重ね合わせた。これを、かしめ機によって圧力を加えることで、正極活物質として実施例１で得られたピロリン系ニトロキシド重合体を、負極活物質として金属リチウムを用いた密閉型のコイン型電池を製造した。
このコイン型電池について、電位掃引範囲３．２〜４．２Ｖでのサイクリックボルタモグラムを測定したところ、３．６５Ｖにニトロキシドラジカルのｐ型レドックス由来の酸化還元波が現れ、繰り返し掃引しても酸化還元波は安定していた。また、定電流０．１ｍＡ（電流密度１５０μＡ／ｃｍ２）での充放電曲線を測定したところ、３．６４Ｖにプラトー電位が現れ、５００サイクル後も顕著な容量低下は見られず、安定な充放電挙動を示した。また、充放電曲線より求めたラジカル材料あたりの容量は１４０ｍＡｈ／ｇであった。[Example 4] (Battery using electrode active material containing pyrroline-based nitroxide polymer)
0.01 g of the pyrroline nitroxide polymer obtained in Example 1, 0.08 g of vapor-grown carbon fiber as an auxiliary conductive material, and 0.01 g of polyvinylidene fluoride as a binder were weighed, and N-methylpyrrolidone was added. It was added and kneaded using an agate mortar. A slurry-like mixture obtained by wet mixing for about 10 minutes was applied on an aluminum foil and stretched, and then dried in a vacuum at 60 ° C. overnight. Thereafter, a coin electrode was molded by punching into a circle having a diameter of 12 mm. The mass of this electrode was 13.0 mg.
Next, the obtained electrode was immersed in an electrolytic solution, and the electrolytic solution was infiltrated into voids in the electrode. As the electrolytic solution, an ethylene carbonate / diethyl carbonate mixed solution (mixing volume ratio 1: 1) containing 1.0 mol / L LiPF 6 electrolyte salt was used. The electrode impregnated with the electrolytic solution was placed on a stainless steel sheath (manufactured by Hosen Co., Ltd.) also serving as a positive electrode current collector, and a polypropylene porous film separator impregnated with the electrolytic solution was laminated thereon. Furthermore, the lithium disk used as a negative electrode was laminated | stacked, and the negative electrode side stainless steel exterior (made by Hosen Co., Ltd.) was piled up in the state which has arrange | positioned the insulating packing around. By applying pressure with a caulking machine, a sealed coin-type battery using the pyrroline nitroxide polymer obtained in Example 1 as the positive electrode active material and metallic lithium as the negative electrode active material was produced.
When a cyclic voltammogram of this coin-type battery was measured in the potential sweep range of 3.2 to 4.2 V, an oxidation-reduction wave derived from the p-type redox of the nitroxide radical appeared at 3.65 V, and it was oxidized even after repeated sweeps. The reduction wave was stable. Further, when a charge / discharge curve at a constant current of 0.1 mA (current density of 150 μA / cm 2 ) was measured, a plateau potential appeared at 3.64 V, and no significant decrease in capacity was observed even after 500 cycles, and stable charge and discharge were observed. The discharge behavior was shown. Moreover, the capacity | capacitance per radical material calculated | required from the charging / discharging curve was 140 mAh / g.
［比較例１］
実施例４において、実施例１で得られたピロリン系ニトロキシド重合体０．０１ｇを、製造例２で得られたポリメタクリル酸ニトロキシド化合物０．０１ｇに変更した以外は実施例４と同様の方法にて、コイン型電池を作成した。
得られたコイン型電池について、実施例４と同様の方法にて充放電曲線を測定した。充放電曲線より求めたラジカル材料あたりの容量は、５４ｍＡｈ／ｇであった。[Comparative Example 1]
In Example 4, the same method as in Example 4 except that 0.01 g of the pyrroline nitroxide polymer obtained in Example 1 was changed to 0.01 g of the polymethacrylic acid nitroxide compound obtained in Production Example 2. A coin-type battery was created.
About the obtained coin-type battery, the charge / discharge curve was measured by the same method as Example 4. The capacity per radical material determined from the charge / discharge curve was 54 mAh / g.
本発明によれば、大きな電流を取り出すことができ、かつ、繰り返し充放電を行っても容量の低下が少ない電池の電極材料として用いられるピロリン系ニトロキシド重合体、当該重合体を含有する電極活物質および当該電極活物質を用いた電池を提供することができる。 According to the present invention, a pyrroline-based nitroxide polymer that can be used as an electrode material for a battery that can take out a large current and has little decrease in capacity even after repeated charge and discharge, and an electrode active material containing the polymer In addition, a battery using the electrode active material can be provided.
１ ステンレス外装
２ 絶縁パッキン
３ 負極
４ セパレータ
５ 正極
６ 正極集電体
DESCRIPTION OF SYMBOLS 1 Stainless steel exterior 2 Insulation packing 3 Negative electrode 4 Separator 5 Positive electrode 6 Positive electrode collector
Claims (4)
A battery using the electrode active material according to claim 3.
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|---|---|
| US (1) | US20120095179A1 (en) |
| JP (1) | JP5527667B2 (en) |
| CN (1) | CN102348727A (en) |
| WO (1) | WO2010104002A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2012133204A1 (en) * | 2011-03-31 | 2014-07-28 | 学校法人早稲田大学 | battery |
| US9356292B2 (en) | 2011-03-31 | 2016-05-31 | Sumitomo Seika Chemicals Co., Ltd. | Radical composition and battery using same |
| JP6069787B2 (en) * | 2012-03-08 | 2017-02-01 | 学校法人早稲田大学 | Benzodithiophenequinone polymer, charge storage material, electrode active material, electrode, and battery |
| US20160218354A1 (en) * | 2013-09-09 | 2016-07-28 | Universite Catholique De Louvain | Hybrid Electrode For Non-Aqueous Electrolyte Secondary Battery |
| DE102014003300A1 (en) | 2014-03-07 | 2015-09-10 | Evonik Degussa Gmbh | New tetracyanoanthraquinone dimethyne polymers and their use |
| DE102014004760A1 (en) | 2014-03-28 | 2015-10-01 | Evonik Degussa Gmbh | New 9,10-bis (1,3-dithiol-2-ylidene) -9,10-dihydroanthracene polymers and their use |
| JP6533303B2 (en) | 2015-08-26 | 2019-06-19 | エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ | Use of certain polymers as charge storage |
| EP3135704A1 (en) | 2015-08-26 | 2017-03-01 | Evonik Degussa GmbH | Use of certain polymers as charge storage |
| EP3262668B1 (en) | 2015-08-26 | 2018-12-05 | Evonik Degussa GmbH | Use of certain polymers as a charge store |
| EP3136410A1 (en) | 2015-08-26 | 2017-03-01 | Evonik Degussa GmbH | Use of certain polymers as charge storage |
| JP6720350B2 (en) | 2016-06-02 | 2020-07-08 | エボニック オペレーションズ ゲーエムベーハー | Method for manufacturing electrode material |
| US11289700B2 (en) | 2016-06-28 | 2022-03-29 | The Research Foundation For The State University Of New York | KVOPO4 cathode for sodium ion batteries |
| TWI686415B (en) | 2016-08-05 | 2020-03-01 | 德商贏創運營有限公司 | Use of thianthrene-containing polymers as charge storage means |
| EP3279223A1 (en) | 2016-08-05 | 2018-02-07 | Evonik Degussa GmbH | Use of polymers containing thianthrene as charge storage |
| JP6650054B2 (en) | 2016-09-06 | 2020-02-19 | エボニック オペレーションズ ゲーエムベーハー | Improved oxidation of secondary amino groups |
| DE102017005924A1 (en) | 2017-06-23 | 2018-12-27 | Friedrich-Schiller-Universität Jena | Use of benzotriazinyl-containing polymers as charge storage |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3687736B2 (en) * | 2000-02-25 | 2005-08-24 | 日本電気株式会社 | Secondary battery |
| DE10027744A1 (en) * | 2000-06-05 | 2001-12-06 | Bayer Ag | Production of polymers by controlled living radical polymerization of vinyl monomers in aqueous solution involves using the monomers, initiator or radical trapping species in the form of a cyclodextrin complex |
| JP4918733B2 (en) * | 2000-10-05 | 2012-04-18 | 日本電気株式会社 | Secondary battery and manufacturing method thereof |
| JP2002170568A (en) * | 2000-12-01 | 2002-06-14 | Nec Corp | Battery |
| JP4830207B2 (en) * | 2001-03-30 | 2011-12-07 | 日本電気株式会社 | battery |
| JP4687848B2 (en) * | 2001-04-03 | 2011-05-25 | 日本電気株式会社 | Power storage device |
| JP4967211B2 (en) * | 2001-09-26 | 2012-07-04 | 日本電気株式会社 | Photoelectrochemical device |
| JP2003132891A (en) * | 2001-10-23 | 2003-05-09 | Nec Corp | Secondary battery |
-
2010
- 2010-03-05 JP JP2011503792A patent/JP5527667B2/en not_active Expired - Fee Related
- 2010-03-05 US US13/255,439 patent/US20120095179A1/en not_active Abandoned
- 2010-03-05 WO PCT/JP2010/053617 patent/WO2010104002A1/en active Application Filing
- 2010-03-05 CN CN2010800113508A patent/CN102348727A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2010104002A1 (en) | 2012-09-13 |
| US20120095179A1 (en) | 2012-04-19 |
| WO2010104002A1 (en) | 2010-09-16 |
| CN102348727A (en) | 2012-02-08 |
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